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arXiv:cond-mat/9811277 · The Journal of Chemical Physics

Stochastic Liouvillian algorithm to simulate dissipative quantum dynamics with arbitrary precision

Jürgen T. Stockburger, Chi H. Mak

Published Mar 15, 1999• 87 citations
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Abstract

An exact and efficient new method to simulate dynamics in dissipative quantum systems is presented. A stochastic Liouville equation, deduced from Feynman and Vernon’s path-integral expression of the reduced density matrix, is used to describe the exact dynamics at any dissipative strength and for arbitrarily low temperatures. The utility of the method is demonstrated by applications to a damped harmonic oscillator and a double-well system immersed in an Ohmic bath at low temperatures.

DOI
10.1063/1.478396

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•Jan 20, 2005•0 citations
An exact and efficient new method to simulate dynamics in dissipative quantum systems is presented. A stochastic Liouville equation, deduced from Feynman and Vernon’s path-integral expression of the reduced density matrix, is used to describe the exact dynamics at any dissipative strength and for arbitrarily low temperatures. The utility of the method is demonstrated by applications to a damped harmonic oscillator and a double-well system immersed in an Ohmic bath at low temperatures.
Classical Brownian motion has well been investigated since the pioneering work of Einstein, which inspired mathematicians to lay the theoretical foundation of stochastic processes. A stochastic formulation for quantum dynamics of dissipative systems described by the system-plus-bath model has been developed and found many applications in chemical dynamics, spectroscopy, quantum transport, and other fields. This article provides a tutorial review of the stochastic formulation for quantum dissipative dynamics. The key idea is to decouple the interaction between the system and the bath by virtue of the Hubbard-Stratonovich transformation or Itô calculus so that the system and the bath are not directly entangled during evolution, rather they are correlated due to the complex white noises introduced. The influence of the bath on the system is thereby defined by an induced stochastic field, which leads to the stochastic Liouville equation for the system. The exact reduced density matrix can be calculated as the stochastic average in the presence of bath-induced fields. In general, the plain implementation of the stochastic formulation is only useful for short-time dynamics, but not efficient for long-time dynamics as the statistical errors go very fast. For linear and other specific systems, the stochastic Liouville equation is a good starting point to derive the master equation. For general systems with decomposable bath-induced processes, the hierarchical approach in the form of a set of deterministic equations of motion is derived based on the stochastic formulation and provides an effective means for simulating the dissipative dynamics. A combination of the stochastic simulation and the hierarchical approach is suggested to solve the zero-temperature dynamics of the spin-boson model. This scheme correctly describes the coherent-incoherent transition (Toulouse limit) at moderate dissipation and predicts a rate dynamics in the overdamped regime. Challenging problems such as the dynamical description of quantum phase transition (local- ization) and the numerical stability of the trace-conserving, nonlinear stochastic Liouville equation are outlined.
An effective and flexible numerical scheme is proposed to simulate the dissipative quantum dynamics of a linearized system–bath Hamiltonian. Based on the observation that the Feynman path integrals for a Gaussian bath have a quadratic functional form, the bath average can be performed by directly sampling paths of the discretized harmonic modes and then propagating the system under the influence of quantum Gaussian force. The algorithm is amenable to all known quantum propagation methods and can thus be flexibly applied to study quantum dissipation in the condensed phase. Nontrivial numerical examples based on the spin-boson and damped quantum oscillator models are presented to demonstrate the application of the new algorithm.
We extend a standard stochastic theory to study open quantum systems coupled to a generic quantum environment. We exemplify the general framework by studying a two-level quantum system coupled bilinearly to the three fundamental classes of non-interacting particles: bosons, fermions, and spins. In this unified stochastic approach, the generalized stochastic Liouville equation (SLE) formally captures the exact quantum dissipations when noise variables with appropriate statistics for different bath models are applied. Anharmonic effects of a non-Gaussian bath are precisely encoded in the bath multi-time correlation functions that noise variables have to satisfy. Starting from the SLE, we devise a family of generalized hierarchical equations by averaging out the noise variables and expand bath multi-time correlation functions in a complete basis of orthonormal functions. The general hierarchical equations constitute systems of linear equations that provide numerically exact simulations of quantum dynamics. For bosonic bath models, our general hierarchical equation of motion reduces exactly to an extended version of hierarchical equation of motion which allows efficient simulation for arbitrary spectral densities and temperature regimes. Similar efficiency and flexibility can be achieved for the fermionic bath models within our formalism. The spin bath models can be simulated with two complementary approaches in the present formalism. (I) They can be viewed as an example of non-Gaussian bath models and be directly handled with the general hierarchical equation approach given their multi-time correlation functions. (II) Alternatively, each bath spin can be first mapped onto a pair of fermions and be treated as fermionic environments within the present formalism.
Half century has past since the pioneering works of Anderson and Kubo on the stochastic theory of spectral line shape were published in J. Phys. Soc. Jpn. 9 (1954) 316 and 935, respectively. In this review, we give an overview and extension of the stochastic Liouville equation focusing on its theoretical background and applications to help further the development of their works. With the aid of path integral formalism, we derive the stochastic Liouville equation for density matrices of a system. We then cast the equation into the hierarchy of equations which can be solved analytically or computationally in a nonperturbative manner including the effect of a colored noise. We elucidate the applications of the stochastic theory from the unified theoretical basis to analyze the dynamics of a system as probed by experiments. We illustrate this as a review of several experimental examples including NMR, dielectric relaxation, Mössbauer spectroscopy, neutron scattering, and linear and nonlinear laser spectroscopies. Following the summary of the advantage and limitation of the stochastic theory, we then derive a quantum Fokker–Planck equation and a quantum master equation from a system–bath Hamiltonian with a suitable spectral distribution producing a nearly Markovian random perturbation. By introducing auxiliary parameters that play a role as stochastic variables in an expression for reduced density matrix, we obtain the stochastic Liouville equation including temperature correction terms. The auxiliary parameters may also be interpreted as a random noise that allows us to derive a quantum Langevin equation for non-Markovian noise at any temperature. The results afford a basis for clarifying the relationship between the stochastic and dynamical approaches. Analytical as well as numerical calculations are given as examples and discussed.
Complex quantum phenomena can often be understood more easily by identifying a relevant system and an environment which interacts with the system. Numerically exact methods for these dissipative quantum systems are discussed with particular focus on their dynamics. Using the dissipative two‐state system and charge transport through a mesoscopic metallic island as illustrative examples, we present algorithms based on the importance sampling of Feynman path integrals as well as novel techniques relying on the numerical simulation of stochastic Liouville‐von Neumann equations.
In this thesis the path integral formalism is applied to the calculation of the dynamics of dissipative quantum systems. The time evolution of a system of bilinearly coupled bosonic modes is treated using the real-time path integral technique in coherent-state representation. This method is applied to a damped harmonic oscillator within the Caldeira-Leggett model. In order to get the stationary trajectories the corresponding Lagrangian function is diagonalized and then the path integrals are evaluated by means of the stationary-phase method. The time evolution of the reduced density matrix in the basis of coherent states is given in simple analytic form for weak system-bath coupling, i.e. the so-called rotating-wave terms can be evaluated exactly but the non-rotating-wave terms only in a perturbative manner. The validity range of the rotating-wave approximation is discussed from the viewpoint of spectral equations. In addition, it is shown that systems without initial system-bath correlations can exhibit initial jumps in the population dynamics even for rather weak dissipation. Only with initial correlations the classical trajectories for the system coordinate can be recovered. The path integral formalism in a combined phase-space and coherent-state representation is applied to the problem of curve-crossing dynamics. The system of interest is described by two coupled one-dimensional harmonic potential energy surfaces interacting with a heat bath. The mapping approach is used to rewrite the Lagrangian function of the electronic part of the system. Using the Feynman-Vernon influence-functional method the bath is eliminated whereas the non-Gaussian part of the path integral is treated using the perturbation theory in the small coordinate shift between potential energy surfaces. The vibrational and the population dynamics is considered in a lowest order of the perturbation. The dynamics of a Gaussian wave packet is analyzed along a one-dimensional reaction coordinate. Also the damping rate of coherence in the electronic part of the relevant system is evaluated within the ordinary and variational perturbation theory. The analytic expressions for the rate functions are obtained in the low and high temperature regimes.